Mercuri alkyl phenol derivatives



Patented Aug. 19, 1941 UNITED STATES Pl k'l'El' l'l' OFFICE MERC URI ALKYL PHENOL DERIVATIVES Walter G. Christiansen, Glen Ridge, N. J., assignor to E. R. Squibb &

poration of New York No Drawing. Application November 22, 1938,

Serial No. 241,727

Claims.

wherein R represents a lower alkyl, preferably methyl, Y is a member of the group consisting of chloro and nitro, X is a member of the group consisting of halogen and nitro, one R represents a lower alkyl, preferably methyl, and the other R. represents a lower-preferably branched chainalkyl having at least three carbon atoms. They may be prepared by interacting the corresponding unmercurated alkyl phenol derivatives with mercuric acetate, and replacing the acetoxy with the desired anion by means of the compound of that anion with an alkali metal (of. Whitmores Organic Compounds of Mercury, 1921, pp. 257, 258). These mercuri phenol derivatives have been found to be active germicides.

' The following examplesare illustrative of the invention: 4 l l EXAMPLE 1 Anhydro-mercuri 4-ehZ0ro 3,6- dimethyZ phenol 4 g. 4-chloro 3,6-dimethyl phenol is dissolved in cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 8 g. mercuric acetate dissolved in 20 cc. water slightly acidulated with acetic acid is added rapid-dropwise with mechanical stirring. After one and one-half hours of refluxing, a test for divalent mercury being negative and heavy White crystals having formed, the mixture is filtered; the residue, upon being washed successively with methyl alcohol, water, and methyl alcohol, and dried, is found to be soluble in dilute alkali.

alkaline with dilute alkali,

Sons, New York, N. Y., a cor- EXAMPLEZ Anhydro-mercuri 4-chl0ro 3,5-dimethyl phenol This compound is prepared precisely in accordance with the preceding example except that 4-chloro 3,5-dimethyl phenol is substituted for chloro 3,6-dimethyl phenolv EXAMPLE 3 4-ehloro 3,5-di1nethyl phenol 20 grams of 4-chloro 3,5-dimethyl phenol are dissolved in cc. of methyl alcohol. The solution is filtered and heated to boiling whereupon a solution of 40 grams of mercuric acetate in 100 cc. of water, acidified by adding 1.7 cc. of acetic acid, are added. The mixture is then boiled under reflux until it no longer contains any inorganic mercury. The mixture is cooled and the solid which separates is collected on a filter, washed once with methyl alcohol, twice with water and twice more with methyl alcohol.

The solid, undried, is next suspended in a solution of 26 grams of sodium hydroxide in 500 cc. of water and stirred for two hours. Then 33 cc. of glacial acetic acid are stirred in for .15 minutes. The solid is then collected on a filter and washed with water until adhering sodium acetate and excess acetic acid have been removed, and finally dried at 100 C.

EXAMPLE 4 Acetoxymercuri B-methyl 4-chloro t-isopropyl phenol 9.25 g. 3-methyl 4-chloro fi-isopropyl phenol is dissolved in 50 cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 14.7 g. mercuric acetate dissolved in 50 cc. water slightly acidulated with acetic acid is added. After five hours of refluxing, a test for divalent mercury being negative, the reaction mixture is filtered, washed, and dried as in Example 1, yielding the desired compound in the form of white crystals.

EXAMPLE 5 Hydromy mercuri 3-isopropyl 4-chlor0 6-methyl phenol A solution of 8 g. 3-isopropyl 4-chloro S-methyl phenol in cc. ethyl alcohol is treated in the manner of Example 1 with 12.5 g. mercuric acetate in 45 cc. water. After twelve hours of refiuxing, a test for divalent mercury being slightly positive and some crystals having formed, the mixture is filtered. The filtrate is made strongly and the grayish Z-anhydro-mercuri Acetorymercuri 2-nitro-3,fi-dimethyl phenol 2.19 g. Z-nitro 3,6-dimethyl phenol is dissolved in 13 cc. methyl alcohol, and while thesolutionis refluxed on a steam-bath, 3.93 g. mercuric acetate dissolved in 13 cc. water slightly acidulated with acetic acid is added. After seven hours of refluxing, a test for divalent mercury being negative, the reddish-brown crystalprecipitate, the desired compound, is filtered, washed, andidriedf as in Example 1, and is found to give a. light-red solution with dilute alkali.

EXAMPLE 7 Acetorymercmi 3-methyl 4'-m'tro" 6 isopropyl phenol 2.5 g. 3-methyl 4 nitro-6-isopropy1 phenol is dissolved'in 13cc. methyl alcohol, and while the solution is refluxed on a steam-bath, 4 g. mercuric acetate dissolved in- 12 cc. water slightly acidulatedwith acetic acidisadded. After seven hours of refluxing, a test for divalent mercury being, negative, the. crystalline yellowish precipitate, therdesired compound, is'isolatedasin Example 1, and found to. give an orange solution with dilute. alkalL.

The invention is, of course; not restricted to the above-described: specific compounds. Thus, compoundswhereinR. and R represent a lower alkyl? other than those occurr-ing in the abovedescribed specific compounds. may be prepared by mercurating halo or nitro phenols embodying the desired alkyls, e. g. ethyl, propyl butyl; isobutyl, amyl, isoamyl, etc. Also, compounds wherein X-isa halogen other than chloro may be preparedby using the corresponding-e. g.

bromo-r-eact'ant.

Among the numerous other mercuri-derivatives-that may be prepared in accordance with the invention arethe chloro-, cyano-, thiocyano-, and nitrato-mercuri derivatives, which are formed by treating a; solution of the acetoxymercuri derivative with, respectively, the chloride, cyanide,- thiocyanide and nitrate of" analkali metal.

, The invention may bevariously otherwise. embodied, within the scope of the. appended claims.

I. claim:

1. A compound of the. general. formula (lower alkyl) (lower alkyl) (lower alkyl) H -anion (halogen) g (lower alkyl) wherein at least one of the lower alkyl radicals has at least three carbon atoms.

3. A compound of the general formula (lawmg g -Hg-anion.

r /(lower alkyl).

wherein at least one ofthe lower alkyl radicals has at least three carbon atoms.

4i A compound. of the general. formula.

wherein Y represents a member; of the group consistingi'of' halogen and nitro, and at least one of the lower alkyl radicals has atI least three carbon atoms.

5. A compound of the group consisting of (lowe'ralky-D- and (lower alkyg: Hgh

. -(lo wen alkyl);

wherein Y represents a member of the group consisting of halogen and nitro, and at leastone of the lower alkyl radicalshas at least three carbon atoms.

WALTER: G. CHRISTIANSEN; 

